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CN101622278A - Be used for ethylene homo and with the single component initiator that does not contain phosphine of functionalized comonomer copolymerization - Google Patents

Be used for ethylene homo and with the single component initiator that does not contain phosphine of functionalized comonomer copolymerization Download PDF

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CN101622278A
CN101622278A CN200780052016A CN200780052016A CN101622278A CN 101622278 A CN101622278 A CN 101622278A CN 200780052016 A CN200780052016 A CN 200780052016A CN 200780052016 A CN200780052016 A CN 200780052016A CN 101622278 A CN101622278 A CN 101622278A
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吉勒莫·C·巴赞
勒内·罗贾斯
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University of California
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    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
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Abstract

The invention discloses the novel method that does not contain the non-ionic type list catalyzer of phosphine and make this catalyzer, described catalyzer is used for alkene such as ethene, the homopolymerization of alpha-olefin and the copolymerization of alkene and functional olefines, and need not to use extra coactivator.These non-ionic type list catalyzer that do not contain phosphine also have activity for alkene and the monomeric copolymerization with polar functional group.Catalyzer of the present invention forms for the body part by the rear transition metal with chelating single anion type part, radicals R and neutral bielectron.Catalyzer is prepared as follows: as in the presence of based on the part of nitrogen, benzyl halide (halogen=Cl, Br or I) oxidation adds on the suitable source metal, adds subsequently and takes off the chelating ligand of proton form at stablizer.

Description

Be used for ethylene homo and with the single component initiator that does not contain phosphine of functionalized comonomer copolymerization
The cross reference of related application
The application is the part continuation application of submitting on February 28th, 2003 that is numbered 10/378,957 U.S. Patent application that is numbered 10/377,491 U.S. Patent application and submitted on March 3rd, 2003, and these two pieces of patent applications are incorporated herein by reference.
Technical field
Present invention relates in general to the polymerization of alkene and alkene and functionalized monomer's copolymerization, more specifically, the present invention relates to use the olefinic polymerization of the non-ionic type rear transition metal single component catalyst that does not contain phosphine and alkene and functionalized monomer's copolymerization and need not to use the method for coactivator.
Background technology
In recent years, reported that several are used for the catalyzer of olefinic polymerization.The polymerizing catalyst of Brookhart report methylaluminoxane and lewis acidic in the presence of use (1)Some patents (referring to WO09623010 and reference wherein) have been submitted to based on these catalyzer.These catalyst systems be heat-labile and by methylaluminoxane activatory activity of such catalysts 60 ℃ of down rapidly decay (2), and at room temperature decompose by borine activatory catalyzer (3)The catalyzer of another type is those of people such as Younkin report (4)These catalyzer are not for needing the neutral substance of activator.Yet, to compare with cationic Brookhart system, they often have inductive phase and activity lower.PCT application WO01/92348 has described vinyl polymerization and the ethylene copolymer that uses the amphoteric ion type nickel complex that needs the Lewis acid existence.Lewis acid is that functional group (functionality) institute's deactivation and their promote the side reaction do not expected, for example to the polymer chain deleterious chain transfer of growing.
Although the problems referred to above are arranged, in academic and industrial laboratories, the interest that has metal to participate in the olefinic polymerization of (mediate) is not still subtracted (5,6,7,8,9,10,11,12,13,14)And, although the problems referred to above are arranged, in this field for lower total cost being provided and providing the single component catalyst system of better control to have demand to polyreaction.
Summary of the invention
The present invention uses the non-ionic catalyst do not contain phosphine to satisfy the two demand of the copolymerization process of the homopolymerization method of ethene and ethene and functionalized comonomer, and does not need extra coactivator.
Catalyzer of the present invention has following general formula:
Figure A20078005201600071
Wherein:
M represents the rear transition metal ion, and it preferably is selected from Fe, Co, Ni, Pd and Cu.
A, B and C ' expression oxygen, nitrogen, phosphorus, carbon or sulphur atom.
L represents that saturated or undersaturated bridge joint hydrocarbon unit is-(CH 2) n(n=0～3) ,-CH=CH-and aromatic units.
R represents to be selected from the C of the aryl of alkyl, alkenyl (alkene), alkyl, cycloalkyl, aryl or replacement 1～C 24Hydrocarbon; And described aryl substituent can be the functionalized group that makes electron density that C ' locates improve or reduce or make the sterically hindered change (modify) that C ' locates.
R ' expression is by those represented hydrocarbon of R, but R needn't be identical with R '.
" expression is selected from the hydrocarbon C of the aryl that the aryl, O-hydrocarbon, O-aryl, O-of alkyl, alkenyl, alkyl, cycloalkyl, aryl, replacement replace to R 1～C 24Hydrocarbon; And described substituting group can be halogen.
The neutral monodentate bielectron of L ' expression give the body part based on nitrogen.
L ' can represent that also the part based on oxygen of neutral monodentate bielectron is O=P (R Iv) 3, R IvCOR Iv, furans, R IvOR Iv, 1,4-diox, (R Iv) 3NO.
R IvThe aryl of expression hydrogen, hydrocarbon, alkyl, alkenyl, alkyl, cycloalkyl, aryl or replacement.
R ' " (the C=O)-aryl of benzyl, (C=O)-alkyl, (C=O)-aryl or the replacement of the aryl of expression hydrocarbon, alkyl, alkenyl, alkyl, allyl group, aryl, replacement, benzyl, replacement.
" and L can be combined into single chelating moiety (fragment) to R '.
Only when A=phosphorus, carbon or nitrogen, R v=R.
In one embodiment, do not contain the following formation of non-ionic catalyst of phosphine: in the presence of stablizer such as containing n-donor ligand, alkylogen or acyl halide oxidation add to suitable source metal (that is Ni (COD), 2, Ni (CH 2=C (CH 3) CH 2) 2, Pd (dba) 2, Pd (P (C 4H 9) 3) 2Deng) on; Add the chelating ligand that takes off proton afterwards.
The invention also discloses the described non-ionic catalyst that does not contain phosphine is used for alkene and for example alcohol (preferred 5-norbornylene-2-alcohol) and acetic ester (preferred 5-norbornylene-2-yl acetate) copolymerization of the functionalized monomer with functional group.Other functional group comprise have cyano group, the alkene of ketone group, alkyl halogen, nitro and sulfonate radical (sulfanate) group.
In another embodiment, the present invention uses the non-ionic catalyst that does not contain phosphine to guarantee to make olefinic polymerization, and described alkene is selected from: formula R 1CH=CH 2Compound; Cyclopentenes, vinylbenzene, norbornylene and/or polar olefin such as H 2C=CH (CH 2) nCO 2R 2The cyclopentenes that replaces, the vinylbenzene of replacement, have the norbornene derivative of the replacement of functional group; Perhaps their combination; Wherein, R 1Can be hydrogen, alkyl, have functional group (OH, NH 2Deng) the alkyl of replacement, and R wherein 2Can be hydrogen or alkyl.
These novel single component catalysts provide the convenient route that leads to the polyolefine material with enhanced propertied (for example wetting ability), thereby have significantly improved the effectiveness that these materials are used for various commercial purposes.
Description of drawings
For a more complete understanding of the present invention, carry out following description with reference now to accompanying drawing, wherein:
Fig. 1 shows the synoptic diagram of the molecular structure of drawing of initiator 1 under 50% probability.For the sake of clarity, hydrogen atom is not shown.
Fig. 2 shows the synoptic diagram of the molecular structure of drawing of initiator 2 under 50% probability.For the sake of clarity, hydrogen atom is not shown.
Fig. 3 shows the synoptic diagram of the molecular structure of drawing of initiator 3 under 50% probability.For the sake of clarity, hydrogen atom is not shown.
Fig. 4 shows the synoptic diagram of the molecular structure of drawing of initiator 4 under 50% probability.For the sake of clarity, hydrogen atom is not shown.
Embodiment
The invention provides the novel non-ionic type list catalyzer of phosphine and the method for making this catalyzer of not containing, described single catalyzer is used to make alkene (as ethene, alpha-olefin and functional olefines) homopolymerization and copolymerization, and need not to use extra coactivator.These catalyzer also have activity for alkene and the monomeric copolymerization with polar functional group.
Generally speaking, catalysis initiator of the present invention constitutes for the body part by rear transition metal and chelating single anion type part, radicals R and neutral bielectron.Initiator of the present invention is represented by following overall structure:
Figure A20078005201600091
Wherein:
M represents the rear transition metal ion, and it preferably is selected from Fe, Co, Ni, Pd and Cu.
A, B and C ' expression oxygen, nitrogen, phosphorus, carbon or sulphur atom.
L represents that saturated or undersaturated bridge joint hydrocarbon unit is-(CH 2) n(n=0～3) ,-CH=CH-and aromatic units.
R represents to be selected from the C of the aryl of alkyl, alkenyl, alkyl, cycloalkyl, aryl or replacement 1～C 24Hydrocarbon; And described aryl substituent can be the functionalized group that makes electron density that C ' locates improve or reduce or make the sterically hindered change that C ' locates.
R ' expression is by described those hydrocarbon of R, but R needn't be identical with R '.
" expression is selected from the hydrocarbon C of the aryl that the aryl, O-hydrocarbon, O-aryl, O-of alkyl, alkenyl, alkyl, cycloalkyl, aryl, replacement replace to R 1～C 24Hydrocarbon; Perhaps halogen.
The neutral monodentate bielectron of L ' expression based on nitrogen give the body part, promptly
Figure A20078005201600092
L ' also can represent the part based on oxygen of neutral monodentate bielectron, i.e. O=P (R Iv) 3, R IvCOR Iv, furans, R IvOR Iv, 1,4-diox, (R Iv) 3NO.
R IvThe aryl of expression hydrogen, hydrocarbon, alkyl, alkenyl, alkyl, cycloalkyl, aryl or replacement.
R ' " (the C=O)-aryl of benzyl, (C=O)-alkyl, (C=O)-aryl or the replacement of the aryl of expression hydrocarbon, alkyl, alkenyl, alkyl, allyl group, aryl, replacement, benzyl, replacement.
R ' " and L ' can be combined into single chelating moiety, the example of described chelating moiety is expressed from the next:
n＝1-2
Only when A=phosphorus, carbon or nitrogen, R v=R.
Described initiator is prepared as follows: as in the presence of based on the part of nitrogen, benzyl halide (halogen=Cl, Br or I) oxidation adds on the suitable source metal at stablizer; Add afterwards and take off the chelating ligand of proton form.Described source metal includes, but not limited to Ni (COD) 2, Ni (CH 2=C (CH 3) CH 2) 2, Pd (dba) 2, and Pd (P (C 4H 9) 3) 2In one embodiment, described stablizer is a containing n-donor ligand.
In the presence of disclosed single component catalysis initiator, the polymerization of alkene and copolymerization take place under-30 ℃～100 ℃ temperature.These alkene include, but are not limited to: R 1CH=CH 2Cyclopentenes, vinylbenzene, norbornylene and/or polar olefin such as H 2C=CH (CH 2) nCO 2R 2The cyclopentenes that replaces, the vinylbenzene of replacement, have the norbornene derivative of the replacement of functional group; Wherein, R 1Can be hydrogen, alkyl, have functional group (OH, NH 2Deng) the alkyl of replacement.In a preferred embodiment, the non-ionic catalyst that does not contain trimethyl-phosphine is used for the copolymerization of the pure and mild 5-norbornylene of alkene and 5-norbornylene-2--2-yl acetate.Other functional group comprise have cyano group, the alkene of ketone group, alkylogen/aryl halide, nitro and sulfonate group.In addition, R 2Can be hydrogen or alkyl.
It is to place on the glass fibre and it is transferred to Bruker CCD platform diffractometer by the monocrystalline with described initiator to carry out that the crystallography of these catalysis initiators characterizes.SMART (15)Routine package is used for determination unit-unit cell parameters and carries out data gathering (be 25 seconds/frame the sweep time of ball diffraction data).Original frame data is used SAINT (16)And SADABS (17)Handle, produce the reflectance data file.Subsequent calculations is used SHELXTL (18)Program is carried out.Structure is resolved by direct method and is passed through full matrix (full-matrix) technics of least squares according to F 2Carry out refine (refine).The analysis scattering factor that in whole analysis, is used for neutral atom (19)Hydrogen atom is by difference-fourier spectra location and to its refine (x, y, z and U Iso) (20)Evaporation or the diffusion of pentane in benzene or toluene solution by benzene obtain to be suitable for the initiator 1,2 of x ray diffraction studies and 4 monocrystalline.
The NMR spectrum of catalysis initiator 1～4 uses Varian Unity 400 and 500 spectrometers to obtain. 1The HNMR sample uses the 10mg sample in 1mL d-benzene to prepare under inert conditions. 13The CNMR sample be used for 1The similar mode of the sample of H NMR prepares, but is to use the 25mg sample.All NMR samples all at room temperature use.
Polymer samples by under 135 ℃, in orthodichlorobenzene, with respect to the gpc analysis according to the universal calibration of polystyrene standards characterize (in the polymkeric substance laboratory, the high temperature chromatogram, PI-GPC200).Sample is prepared as follows: weighing 6.5～8mg polymkeric substance and they are dissolved in the 5mL orthodichlorobenzene under 135 ℃.Sample then under 135 ℃ the lamination teflon filter by 1 μ m be filled in the bottle of band cap (21)
The NMR spectrum of copolymer sample is to use Varian Unity 500 spectrometers to obtain.Polymkeric substance 1H NMR spectrum is to use 25～30mg to be dissolved in the mixed solvent (C of 1: 4 volume ratio down at 115 ℃ 6D 6/ 1,2,4-trichlorobenzene) polymkeric substance in obtains.What the integration at the integration at functional group peak/skeleton peak obtained is: in per 1000 carbon units, be incorporated into intraskeletal monomeric percentage ratio (21)
Following examples will describe best practice of the present invention.
Embodiment 1
Catalysis initiator 1:N-(2, the 6-diisopropyl phenyl)-2-(2,6-diisopropyl phenyl imino-) propionamido-(propanamidato)-κ 2N, O (η 1-CH 2Ph) nickel (pyridine)
Synthesizing under inert atmosphere of initiator 1 carried out, and minimally is exposed to light.Under 35 ℃ or envrionment temperature, with benzyl chloride (63mg, 0.63mmol) and pyridine (234mg, 2.96mmol) the mixture process Ni in 2mL THF (COD) 2Solution (68mg, 0.25mmol is in 5mL THF).The sylvite (108mg, 0.24mmol are dissolved among the 3mL THF) that adds part after 10 minutes.Make reaction mixture be warming up to room temperature and stirred overnight, removing volatiles under vacuum then.Gained oily matter filters with ether (15mL) extraction and to it.Initiator 1 separates from first crystallization batch (batch) with 62% productive rate as the darkorange crystal. 1H NMR spectrum demonstrates two kinds of isomer of 3: 1 ratios, and it is to have N, the coordination of O part and benzyl are in cis or trans position of orientation with respect to the carboxamide group positional isomers.
1H-NMR (399.95MHz, [d 6]-benzene, 298K): main isomer; δ=7.91 (d, 1H), 7.40 (d, 1H), 7.14-6.95 (m, 6H), 6.80-6.73 (m, 3H), 6.71-6.63 (m, 3H), 6.24 (t, 1H), 5.83 (t, 2H), 3.90 (sep 2H), 3.54 (sep 2H), 2.09 (s, 3H), 1.58 (dd 12H), 1.39 (d, 12H), 1.42 (s, 2H), less important isomer; (3.64 sep 2H), 3.31 (sep 2H), 2.07 (s, 3H), 1.40 (d, 12H, CH 3-i-Pr), 1.17 (d, 6H, CH 3-i-Pr).
The monocrystalline of initiator 1 that is suitable for Crystallographic Study, and the results are shown among Fig. 1 by obtaining in the benzene by at room temperature slowly evaporating.Molecular connectivity and N, the O-coordination structure is consistent and support described 1The mensuration (assignment) of H-NMR spectrum.Pros-the planar geometry that around Ni, has distortion.Benzyl is with η 1The mode coordination, and methylene radical is in trans direction with respect to the nitrogen-atoms of carboxamide.Benzyl moiety is with respect to being tilted 7 ° by the plane that N (1)-Ni-O limits.169.87 (10) ° N (1)-Ni-N (3) angle is left 10 ° of N (1)-Ni-O plane less than 180 ° and N (3) atom.The bond length of Ni-O (1), Ni-N (1), Ni-C (28) and Ni-N (3) is respectively
Figure A20078005201600121
With
Figure A20078005201600122
Embodiment 2
Catalysis initiator 2:[N-(2, the 6-diisopropyl phenyl)-2-(2,6-diisopropyl phenyl imino-) propionamido--κ 2N, O] (η 1CH 2Ph) nickel (2, the 6-lutidine)
Synthesizing under inert atmosphere of initiator 2 carried out, and minimally is exposed to light.Under 35 ℃ or envrionment temperature, with benzyl chloride (63mg, 0.63mmol) and lutidine (156mg, 1.45mmol) the mixture process Ni in 2mL THF (COD) 2Solution (68mg, 0.25mmol is in 5mL THF).The sylvite (108mg, 0.24mmol are dissolved among the 3mL THF) that adds part after 10 minutes.Make reaction mixture be warming up to room temperature and stirred overnight, removing volatiles under vacuum then.Gained oily matter filters with ether (15mL) extraction and to it.Reduce the solvent volume and the crystallization of at room temperature spending the night.Compound 2 separates from first crystallization batch with 71% productive rate as the darkorange crystal.
1The H-NMR spectrum shows individual isomer. 1H-NMR (399.95MHz, [d 6]-benzene, 298K): δ=7.11-7.04 (m, 5H), 6.90 (t, 1H), 6.75 (t, 1H), 6.58-6.50 (m, 4H), 6.23 (t, 1H), 5.84 (d, 2H), 3.89 (sep 2H), 3.66 (s, 6H), 3.49 (sep 2H), 2.09 (s, 3.0), 1.61 (d, 6H), 1.42 (s, 2H), 1.40 (d, 12H), 1.17 (d, 6H). 13C-NMR (125.7MHz, [d 6]-benzene, 298K): δ=182.34,158.79,152.24,141.93,140.13,138.64,136.29,127.86,127.04,124.52,122.96,122.88,122.07,29.73,29.20,26.67,24.67,24.34,24.11,21.09,11.66.
Solid-state sign (Fig. 2) and N that initiator 2 is undertaken by the monocrystalline X-ray diffraction, O-ligand unanimity.Initiator 2 is taked pros-plane coordination geometry on every side at the nickel center, and is cis relation between lutidine and the carboxamide nitrogen.Nitrogen-atoms in the lutidine part is shifted to such an extent that be lower than 9 ° on N-Ni-O plane, and the benzyl part is higher than 4 ° on this plane.Compare with those bond lengths of initiator 1, the bond length of Ni-C (28) and Ni-N (3) has been grown approximately Similarly, Ni-N (1) and Ni-O are long respectively With
Figure A20078005201600133
Embodiment 3
Catalysis initiator 3:[N-(2, the 6-diisopropyl phenyl)-2-(2,6-3, the two methyl fluoride phenyliminos of 5-) propionamido--κ 2N, O] (η 1-CH 2Ph) nickel (2, the 6-lutidine)
Figure A20078005201600134
Synthesizing under inert atmosphere of initiator 3 carried out, and minimally is exposed to light.At ambient temperature, with benzyl chloride (63mg, 0.5mmol) and lutidine (160mg, 1.48mmol) the mixture process Ni in 2mLTHF (COD) 2Solution (68mg, 0.25mmol is in 5mL THF).The sylvite (108mg, 0.23mmol are dissolved among the 3mL THF) that adds part after 5 minutes.Reaction mixture stirred overnight, removing volatiles under vacuum then.Gained oily matter filters with ether (15mL) extraction and to it.Solvent is removed by vacuum.Add pentane and crystallization at room temperature 4 hours.Initiator 3 separates from first crystallization batch with 50% productive rate as the darkorange crystal.The monocrystalline of initiator 3 that is suitable for X-ray diffraction studies, and the results are shown among Fig. 3 by obtaining in the ether by at room temperature slowly evaporating.
1H NMR spectrum shows individual isomer. 1H-NMR (399.95MHz, [d 6]-benzene, 298K): δ=8.06 (s, 2H), 8.04 (s, 4H), 6.98 (d, 2H), 6.90 (d, 1H), 6,88 (d, 1H), 6.80-6.77 (m, 3H), 6.75 (d, 2H), 6.63 (t, 2H), 6.29 (dd, 2H), 6.18 (t, 1H), 5.75 (d, 2H), 3.00 (3,6H), 2.93 (sep2H), 1.69 (s, 3.0), 1.19 (d, 12H), 1.08 (s, 2H). 13C-NMR (125.7MHz, [d 6]-benzene, 298K): δ=184.6,162.09,158.97,150.82,145.76,142.51,141.91,138.28,136.52,133.22,132.96,132.64,132.33,130.37,126.78,125.58,123.18,122.78,122.53,121.69,29.43,25.97,23.68,21.93,11.57.
Embodiment 4
Catalysis initiator 4:[N-(2, the 6-diisopropyl phenyl)-2-(2,6-diisopropyl phenyl imino-) propionamido--κ 2N, O] (η 1-benzoyl) nickel (pyridine)
Synthesizing under inert atmosphere of initiator 4 carried out, and minimally is exposed to light.At room temperature, with Benzoyl chloride (58mg, 0.41mmol) and pyridine (130mg, 1.65mmol) the mixture process Ni in 2mL THF (COD) 2Solution (112mg, 0.41mmol is in 5mL THF).After 15 minutes, with the sylvite (140mg, 0.31mmol are dissolved among the 3mL THF) that added part in 45 minutes.Reaction mixture stirred overnight, and removing volatiles under vacuum.Gained oily matter filters with ether (15mL) extraction and to it.Reduce the solvent volume and the crystallization of at room temperature spending the night.The product of first crystallization batch contains the initiator 4 that has impurity.Allow with 54% productive rate by pentane-ether continuous crystallisation and to isolate as darkorange crystalline initiator 4.
1H NMR spectrum demonstrates a kind of isomer. 1H-NMR (399.95MHz, [d 6]-benzene, 298K): δ=8.58 (d, 2H), 8.39-8.36 (tt, 2H), 7.29 (d, 2H), 7.02 (t, 1H), 6.96-6.89 (m, 6H), 6.24 (t, 1H), 5.85 (t, 2H), 3.86 (wide-sep, 2H), 3.61 (sep 2H), (2.12 s, 3.0), 1.46 (d, 12H), 1.25 (m, 6H), 1.11 (d, 6H). 13C-NMR (125.7MHz, [d 6]-benzene, 298K): δ=250.98,184.67,162.60,152.58,151.35,147.13,143.45,140.22,139.18,137.17,131.29,127.71,125.67,124.41,124.19,123.09,29.90,29.56,25.21,24.14,23.59,21.20.
The monocrystalline that is suitable for the initiator 4 of X-ray diffraction studies is obtained by ether by at room temperature slowly evaporating, and the results are shown among Fig. 4.Part is with N, O coordination mode and melts combine.The benzoyl group is with η 1-mode coordination and be positioned at the trans position of acid amides, and carbonyl is perpendicular to the pericentral square plane structure of nickel.Two aromatic rings are also perpendicular to this square plane.The bond length of Ni-N (2) and Ni-O (1) (is respectively
Figure A20078005201600151
With
Figure A20078005201600152
) with initiator 2 in those are similar.Ni-N (3) bond length of two kinds of complex compounds (nickel-lutidine, nickel-pyridine) much at one
Figure A20078005201600153
Embodiment 7
Use catalysis initiator 1-4 to carry out vinyl polymerization
Use the initiator among the embodiment 1-4 to carry out polymerization in the following manner.In glove box, neutral nickel (the II)-imino-carboxamide initiator (compound shown in the embodiment 1-4) and the toluene of pack in autoclave (100mL) an amount of (10 μ mol) makes that the final volume of toluene solution is 30mL.Reactor seals in glove box.Reactor linked to each other with the ethene pipeline and make described gas with the pressure continuously feeding of 100psi～1000psi to reactor.The reaction mixture of this pressurization stirs under 20～100 ℃ variable temp.After the specific reaction times, discharge ethene and add acetone so that polyreaction finishes.Sedimentary polymkeric substance is collected and dried overnight under vacuum by filtering.Following table 1 has been summed up the ethylene polymerization that uses the above-mentioned initiator among the embodiment 1-4 to carry out.(molecular-weight average and PDI measure and described measured value with respect to polystyrene standards) by the gpc analysis in dichlorobenzene under 135 ℃.
Table 1
Project Initiator Temperature of reaction (℃) Active ( a) ??M w( b) ??M w/M n
??1 ??1 ??40 ??60 ??62900 ??1.8
??2 ??2 ??20 ??43 ??124600 ??1.8
??3 ??2 ??40 ??304 ??143460 ??2.2
??4 ??3 ??40 ??280 ??160500 ??1.9
??5 ??4 ??40 ??270 ??145360 ??1.7
( a) kg polymkeric substance/(mol nickel) (hour), polyreaction is carried out under the ethylene pressure of 100psi.
( b) molecular weight of polyethylene polymer is with respect to according to the pervasive correction of polystyrene standards, calculate by Refractive Index GPC Analysis (orthodichlorobenzene, 135 ℃).
Embodiment 8
The copolymerization of ethene and norbornene derivative
Method 1: initially add comonomer
In glove box, packing in the steel reactor, (0.075M～0.5M) and toluene (26g) make that the cumulative volume of toluene solution is 30mL for neutral nickel (II)-imino-carboxamide initiator (compound shown in the embodiment 1-4), 5-norbornylene-2-yl acetate (A) or the 5-norbornylene-2-alcohol (B) of an amount of (10 μ mol).This steel reactor seals in glove box and links to each other with the ethene pipeline.Make ethene with 100psi～400psi continuously feeding to reactor, and the reaction mixture of this pressurization stirs under 20～80 ℃ temperature.After 20 minutes, discharge ethene and add acetone and methyl alcohol so that polyreaction finish.Sedimentary polymkeric substance is collected and drying 12 hours under high vacuum by filtering.Following table 2 has been summed up the copolyreaction of using initiator 2 to carry out.
Table 2
Project Initiator Comonomer concentration (mol/L) Temperature of reaction (℃) Active ( a) ??M w( b) ??M w/M n Introducing degree (mol%) ( c)
??1 ??2 ??A(0.075) ??40 ?160 ??96450 ??1.9 ??8.6
??2 ??2 ??A(0.150) ??40 ?170 ??93160 ??1.8 ??13.0
??3 ??2 ??B(0.075) ??40 ?147 ??88184 ??2.0 ??7.8
??4 ??2 ??B(0.150) ??40 ?48 ??183400 ??5.7 ??13.6
( a) kg polymkeric substance/(mol nickel) (hour), polyreaction is carried out under the ethylene pressure of 100psi.
( b) molecular weight of polyethylene polymer is with respect to according to the pervasive correction of polystyrene standards, calculate by Refractive Index GPC Analysis (orthodichlorobenzene, 135 ℃).
( c) mol% of norbornene introduces degree, its basis 1H-NMR composes (C 6D 6/ orthodichlorobenzene, 120 ℃) calculate.
Method 2: after ethene is caused, add comonomer
Prepare initiator solution as mentioned above, yet described comonomer is to add by feed hopper after after specified time is carried out in the polymerization that makes ethene.Table 3 has been summed up and has been used the ethene that the initiator among the embodiment 1-4 carries out and the copolyreaction of 5-norbornylene-2-yl acetate (A) or 5-norbornylene-2-alcohol (B).Described in method 1, finish polyreaction.
Table 3
Project Initiator Comonomer concentration (mol/L) Temperature of reaction (℃) Active ( a) ??M w( b) ??M w/M n Introducing degree (mol%) ( c)
??1 ??4 ??A(0.075) ??40 ?261 ??125077 ??2.5 ??2.5
??2 ??4 ??A(0.075) ??40 ?323 ??111800 ??2.6 ??2.8
( a) kg polymkeric substance/(mol nickel) (hour), polyreaction is carried out under the ethylene pressure of 400psi.
( b) molecular weight of polyethylene polymer is with respect to according to the pervasive correction of polystyrene standards, measure by Refractive Index GPC Analysis (orthodichlorobenzene, 135 ℃).
( c) mol% of norbornene introduces degree, its basis 1H-NMR composes (C 6D 6/ orthodichlorobenzene, 120 ℃) calculate.
Reference
Following publication is incorporated herein by reference:
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Though described the present invention, it should be understood that can adopt various modifications and variations under the situation that does not depart from the principle and scope of the present invention, this is that those skilled in the art understand easily in conjunction with preferred embodiment.Therefore, can put into practice this modification within the scope of the appended claims.

Claims (15)

1. catalyzer that is used for olefinic polymerization and copolymerization, this catalyzer has following general formula:
Figure A2007800520160002C1
Wherein:
M is the rear transition metal ion,
A is oxygen, nitrogen, phosphorus, carbon or sulphur,
B is oxygen, nitrogen, phosphorus, carbon or sulphur,
C ' is oxygen, nitrogen, phosphorus, carbon or sulphur,
L is saturated or undersaturated bridge joint hydrocarbon or aromatic units,
R is the C that is selected from the aryl of alkyl, alkenyl, alkyl, cycloalkyl, aryl and replacement 1～C 24Hydrocarbon; Wherein, described aryl substituent can be the functionalized group that makes electron density that C ' locates improve or reduce or make the sterically hindered change that C ' locates,
R ' can be R,
R " the hydrocarbon C of the aryl that replaces for the aryl, O-hydrocarbon, O-aryl, O-that is selected from alkyl, alkenyl, alkyl, cycloalkyl, aryl, replacement 1～C 24Hydrocarbon; With the halogen of O-replacement,
The neutral monodentate bielectron of L ' expression based on nitrogen give the body part,
Figure A2007800520160002C2
L ' is for being selected from O=P (R Iv) 3, R IvCOR Iv, furans, R IvOR Iv, 1,4-diox and (R Iv) 3The part based on oxygen of the neutral monodentate bielectron of NO,
R IvBe the aryl of hydrogen, hydrocarbon, alkyl, alkenyl, alkyl, cycloalkyl, aryl or replacement,
R " ' be (the C=O)-aryl of benzyl, (C=O)-alkyl, (C=O)-aryl or replacement of aryl, benzyl, the replacement of hydrocarbon, alkyl, alkenyl, alkyl, allyl group, aryl, replacement,
R " ' and L ' can be combined into single chelating moiety,
Only when A=phosphorus, carbon or nitrogen, R v=R, and
Thereby described catalyzer does not contain phosphine and is non-ionic type.
2. the catalyzer of claim 1, wherein said rear transition metal is selected from Fe, Co, Ni, Pd and Cu.
3. the catalyzer of claim 2, wherein said rear transition metal is Ni.
4. the catalyzer of claim 1, wherein said catalyzer is selected from: N-(2, the 6-diisopropyl phenyl)-2-(2,6-diisopropyl phenyl imino-) propionamido--κ 2N, O (η 1-CH 2Ph) nickel (pyridine), [N-(2, the 6-diisopropyl phenyl)-2-(2,6-diisopropyl phenyl imino-) propionamido--κ 2N, O] (η 1CH 2Ph) nickel (2, the 6-lutidine), [N-(2, the 6-diisopropyl phenyl)-2-(2,6-3, the two methyl fluoride phenyliminos of 5-) propionamido--κ 2N, O] (η 1-CH 2Ph) nickel (2, the 6-lutidine) and [N-(2, the 6-diisopropyl phenyl)-2-(2,6-diisopropyl phenyl imino-) propionamido--κ 2N, O] (η 1-benzoyl) nickel (pyridine).
5. make the method for the non-ionic type single component catalyst that does not contain phosphine that is used for olefinic polymerization and copolymerization, this method comprises:
In the presence of stablizer, provide source metal,
Alkylogen or acyl halide added on the described source metal and
Add the chelating ligand that takes off proton, thereby make the non-ionic catalyst that does not contain phosphine.
6. the method for claim 5, wherein said source metal is selected from Ni (COD) 2, Ni (CH 2=C (CH 3) CH 2) 2, Pd (dba) 2, and Pd (P (C 4H 9) 3) 2
7. the method for claim 5, wherein said stablizer is a containing n-donor ligand.
8. the method for olefinic polymerization and copolymerization comprises:
Make olefinic polymerization and
In the presence of the non-ionic catalyst that does not contain phosphine, carry out described polymerization;
Wherein, described alkene is selected from: formula R 1CH=CH 2Compound; Cyclopentenes, vinylbenzene, norbornylene and/or polar olefin such as H 2C=CH (CH 2) nCO 2R 2The cyclopentenes that replaces, the vinylbenzene of replacement and have the norbornene derivative of the replacement of functional group; Perhaps their combination; In above-mentioned formula, R 1For hydrogen, alkyl, have functional group (OH, NH 2Deng) the alkyl of replacement, R 2Can be hydrogen or alkyl.
9. the method for claim 8, wherein said catalyzer has following general formula:
Figure A2007800520160004C1
Wherein:
M is the rear transition metal ion,
A is oxygen, nitrogen, phosphorus, carbon or sulphur,
B is oxygen, nitrogen, phosphorus, carbon or sulphur,
C ' is oxygen, nitrogen, phosphorus, carbon or sulphur,
L is saturated or undersaturated bridge joint hydrocarbon or aromatic units,
R is the C that is selected from the aryl of alkyl, alkenyl, alkyl, cycloalkyl, aryl and replacement 1～C 24Hydrocarbon; Wherein, described aryl substituent can be the functionalized group that makes electron density that C ' locates improve or reduce or make the sterically hindered change that C ' locates,
R ' can be R,
R " the hydrocarbon C of the aryl that replaces for the aryl, O-hydrocarbon, O-aryl, O-that is selected from alkyl, alkenyl, alkyl, cycloalkyl, aryl, replacement 1～C 24Hydrocarbon; With the halogen of O-replacement,
The neutral monodentate bielectron of L ' expression based on nitrogen give the body part,
L ' is for being selected from O=P (R Iv) 3, R IvCOR Iv, furans, R IvOR Iv, 1,4-diox and (R Iv) 3The part based on oxygen of the neutral monodentate bielectron of NO,
R IvBe the aryl of hydrogen, hydrocarbon, alkyl, alkenyl, alkyl, cycloalkyl, aryl or replacement,
R " ' be (the C=O)-aryl of benzyl, (C=O)-alkyl, (C=O)-aryl or replacement of aryl, benzyl, the replacement of hydrocarbon, alkyl, alkenyl, alkyl, allyl group, aryl, replacement,
R " ' and L ' can be combined into single chelating moiety,
Only when A=phosphorus, carbon or nitrogen, R v=R, and
Thereby described catalyzer does not contain phosphine and is non-ionic type.
10. the method for claim 8, wherein said catalyzer is selected from N-(2, the 6-diisopropyl phenyl)-2-(2,6-diisopropyl phenyl imino-) propionamido--κ 2N, O (η 1-CH 2Ph) nickel (pyridine), [N-(2, the 6-diisopropyl phenyl)-2-(2,6-diisopropyl phenyl imino-) propionamido--κ 2N, O] (η 1CH 2Ph) nickel (2, the 6-lutidine), [N-(2, the 6-diisopropyl phenyl)-2-(2,6-3, the two methyl fluoride phenyliminos of 5-) propionamido--κ 2N, O] (η 1-CH 2Ph) nickel (2, the 6-lutidine) and [N-(2, the 6-diisopropyl phenyl)-2-(2,6-diisopropyl phenyl imino-) propionamido--κ 2N, O] (η 1-benzoyl) nickel (pyridine).
11. the method for claim 8, wherein said method is implemented under-30 ℃ approximately～about 100 ℃ polymerization temperature.
12. the method for claim 8, wherein said polar olefin are H 2C=CH (CH 2) 8CO 2R 6And R wherein 6Be hydrogen, alkyl, the alkyl of replacement that has functional group or their combination, and n is 0～100 integer.
13. pass through the product of the method preparation of claim 8.
14. the method for claim 8, wherein said functional group is alcohol or acetic ester.
15. the method for claim 14, wherein said alcohol are 5-norbornylene-pure and mild described acetic ester is 5-norbornylene-2-base.
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